Dyeing and printing acetyl silk and materials containing it



Patented Feb. 12," 1924.

- cmrao stares; earner caries,

ARTHUR e. GREEN AND KENNETH n. SAUNDERS, on mnncnns'rnn, NGLAND, AS;

SIGNOBS T BRITISH ENG-LAND.

DYESTUFFS CORPORATION WED, 01 :MANGEETEB,

DY EING AND PRINTING ACETYL SILK AND MATERIALS CONTAINING- II.

No Drawing.

To all whom it may concern:

Be it known that we An'rnun Gnonon GREEN and KENNETH HERBERT SAUNDERS,

subjects of the King of England, and resi- 8" dents of Manchester, in the county of Lancashire, England,-have invented certain new and useful Improvements in Dyeing and. Printing Acetyl Silk and Materials Containing It, of which the following is a specifica- 10 tion.

The dyeing or printing of the variety of artificial silk known as F acetyl silk or acetate silk has hitherto presented con-, siderable ditliculties. Those dyestuffs which are readily soluble in water and contain strong salt forming groups, such as sodium salts of sulphonic acids or hydrochlorides of strong colour bases, possess for the most part but little afiinity for this fibreand even when the latter becomes coloured, the dyestufi' can usually be readily removed by soap.

We have now discovered a new method by means of which shades fast to soap and washing can be, roduced upon this fibre with .easily solub e compounds and which further allows of the production of remarkable difi'erential effects with mixedmaterials containing cotton, wool, linen etc., in .combination with acetyl silk. This method can be used in dyeing and in printing; that is, in localized dyeing. l

Thisnew method is based on the fact that whenv the inethyl-omega-sulphonic acids derived from aimdo-azo compounds are treated in .hot aqueous solution especially if it be slightly acid or slightly alkaline theyslowly dissociate with liberation of free amido-azo bases. 'We have found that iL this'is made to occur in the dyebath in presence ofv acetyl-silk, this fibre takes up the sparingly soluble amido-azo compound as. it is produced and becomes dyed therewith yellow, orange, red, etc.. Furthermore, the amido-azo compounds thus fixed on the acetyl silk are. capable of being diazotized upon treatment with nitrous acid and then can be developed like primuline with va rious phenols, amines and amido henols,

- giving a wide range of shades inclu ing, for iristzltince, yellow, orange, red and purple to Application filed March 20,

' cule.

192:. sci-m1 no. saunas.

The methyl-omega-sulphonic acids which we employ for this new method'of'dyeing,j

are azo com ounds containin' the cup NH.CH .;SO I g gr No sulphonic group directly attached to the nucleus should be present. The I 'omega-methyl-sulphonic oup at tached by means of nitrogento t e benzene or naphthalene residue of the amido-azo compound renders the dyestu'fi soluble in water but is s lit ofi' in the dyeing process.

Such dyestu s. may be obtained, for example, by treatin an amido-azo compound with formaldehy e-bisulphite, or by pling an unsulphonated diazo compound with a methyl-omega-sulphonic acid derived from a primary amine of the benzene or naphthalene series produced b treatment of the latter with formaldehy e and 'bisul-- .once or twice in the-mole phite; or by sulphide reduction of a paranitro-derivative. of such an; amido-azamethyl-omega-sul honic acid. Also by cou-.

pling an unsulp onated amine or henol with the diazo compound derived mm a diamine, one amido group of which has been converted into its methyl-omega-sulphonic acid derivative by treatment with formaldehyde and bisulphite. I

In addition to these methyl-.omega-sul-.. phonic acids which are derived from prima rive from mono-alkyl-a'mido-azo bases may also, be used for the'd eing of acetyl sil and the production of ifi'erential effects in dyein mixed materials containing cotton, dinenetc; in combination with acetyl silk. latter dyestuffs so long asthey do not also contain a prima amido group (or a second methyl-omega -su phonic radicle united toa primary amido group}: are insusceptible to diazotization. ey can,

hoseseco'ndary dyestufis which. in addi- Y amido-azo colouring matters those detherefore, be used for "giving their own. i

tion to the methyl-omega-sulphonic radicle attached to the algyl amido group also con-- tain a primary amido group ora secondmethyl-omega sulphonic radicle. attached toa nma amido oup are like the rimdi-y dy e' tufis, cip dble of being diazoti zed andde'velo'ped on e acetyl silk fibre. lhe'y can, therefore, be employed in dyeingin the manner. described for 'the omega-sulfonicv acid dyes.

Compounds of the non-diazotizable type are obtained, for example, by coupling unsulphonated diazo compounds with the reacprimary alkyltion products of sodium formaldehyde bisulphite upon monomethylor monoethylaniline. Compounds of the diazotizable type may be obtained, for example, by sul' phide reduction of the compounds obtained by coupling para-nitrodiazo-benzenechloride with the reaction products of sodium formaldehyde bisulphite upon monomethylpreparation.

For'the most part these dyestuffs have a smaller degree of stability to acids and alkalies than the methyl-omega-sulphonic acids.

In some cases this may be an advantage in enabling dyeing to be effected at a lowel' temperature or in a neutral bath.

The dyestuffs. of the present invention which contain only one azo group, though dyeing acetyl silk, have little or no affinity for cotton and linen. From'a bath containing these dyestuffs therefore a mixed fabric will be selectively dyed, and if a mixture of dyestuffs consisting of one of the said dyestuffs together with a dyestuff' having an aflinity for cotton but little affinity for acetyl silk be used, the acetyl silk fibres will be dyed by the acetyl silk dye, whilst the cotton is dyed by the cotton dyestufi. If the cotton dyestuff' isalso diazotizable, both the colourupon the cotton and that upon the acetyl silk can be developed in different or similar colours according to the choice made of dyestuffs and developers. Furthermore, differential colouring can be obtained by making use of the varying rate of develop ment, the diazo colour upon the cotton beupon the silk. It is thus possible, to develop the former with one developer. As the present dyestuffs can be dyed upon acetyl silk fromaqieutral, acid or alkaline bath, conditions of dyeing can be chosen which are most suitable for thefixation of the other dyestufl upon the cotton, linen or animal fibre.

Sinceother forms of artificial silk such as viscose silk,'behave towards dyestuffs for the slightly alkaline.

most part like cotton, two colour effects such as shots can be produced upon mixed fabwhen the material is washed. When the alkyl-omega sulfonic acid dyestuff' used is a primary one e. is derived from a primary amido-azo compound, the colour produced upon the silk may be converted into other shades by subsequent diazotization and 7 development, employing the same methods as are herein before described for. the dyeing of acetate silk.

Patterns in two colours may be produced with figured material composed of acetate silk woven with cotton, linen or viscose silk, by printing upon such material a thickened paste composed of an alkyl-omega sulfonic acid dycstuff together with a direct cotton colour, the paste being preferably neutral or After printing the material is dried, given a short steaming and then washed or soaped. The-color is fixed upon the'acetate si'lk whilst the direct cotton colour is fixed upon the cotton, linen or viscose silk.

Three or four colour patterns can be produced upon' figured materials of acetate silk and cotton, etc., by firstprinting the material as above with an alkylromega-sulfonic acid dyestuff in conjunction with a direct. cotton colour or alternatively dyeing it with sucha mixture in the manner herein before described, and subsequently cover-printing with a suitable basic dyestuff, with which a discharging agent suchas formosol may or may not beassociated. x

The following examples will serve to illustrate further the nature of this invention Example 1.

which is obtained by heating unsymmrdimethyl-di-p-amido-azobenzene with sodium bisulphite formaldehyde. The bath .is preferably acidified with 1 percent of conbut the invention is not limited thereto I ing developed, for example with B-naphthol, much more rapidly than the acetyl silk dye centrated hydrochloric acid or rendered alkaline with 1 per. cent of soda ash.

' blue. After rinsing in water the silk is- With dimethylanili Red.

. acetoacetic ether; -Orange. mf-amidophenol B1uish-red.' K mhenylene diamine Maroon. amidonaphthol (1: 7 Dark purple. fi-naphthylamine Bluish-red. a-naphthylamine ether Purple to black. phenol Orange-brown. ['l-naphthol Purple. l

a After washing) washed.

silk is dyed a right yellow.

Ewmnple $3.

' The yellow dyed silk obtainedin the pren time example is diazotized by immersion for 15 minutes in a cold bath containing.

3 parts of sodium nitrite and 10 parts of concentrated hydrochloric acid per 1000 parts of water. The colour changes to dark brought into a developing bath, preferably warm, when the followingzcolours are produced according to the develbperchosnzfi-ox naphthoic acid v Navy blue to black.

The silk is allowed to remain in the developing bath from 10 to 30 minutes and is then Example Acetyl silk yarn is dyed asin Example but using a dyestufi of the constitution which is obtained by coupling diazotized para-nitraniline with aniline-methyl-omegasulphonic acid. The silk acquires a bright orange shade. Y

Example 4.

The orange dyed silk obtained in the previous example is diazotized by immersion for fifteen'minutes in a nitrous acid bath made up as in Example 2. After rinsing in water the silk is then brought into a developin bath, when the followin colours are pro uced according'to the deve oper used p ofl" in dilute ammonia th cent to 1 per cent solution, and the silk is vallowed to remain in the bath for 1} hour.

Ewwntplc 5.

i Mercerized cotton cloth containing effect 7 threads of acetyl silk, or hosiery consisting artly of cotton and partly of acetyl silk 1s dyed at 60 to C. in a bath containing a mixture of chlorazol black BH and the dyestuif mentioned in Example 3; 10 per 7 cent of salt and l per cent of sodaash are also added. 'After dyeing andrinsing, the

material is immersed in a nitrous acid hath made u as described in Example 2, and

then, a er washing, in a developing bath conslsting of sodium Li-naphtholate. The

cotton is dyed dark navy blue whilst the silk I becomes bright red.

donaphthol a dark purple is produced upon the silk whilst the cotton is black.

Example 6. g)

If in place of the fi-naphtholate the developer employed is a solution of 1:7 ami- Cotton cloth embroidered with acetyl silk is dyed at 6080 C. f rom abath containing a mixture of primfuline and the dyestufi mentioned in Example 1; 5 per cent of salt and 1 per cent of soda ash being also added.

' The entiremateri'al will now be yellow, the

cotton having been dyed by the 'primuline and the acetyl silk by the other dyestufi'.

Upon immersion in a nitrous acid bath,' made up as described in Example 2, both 1 dyestufi's are diazotized, the primuline changing to a reddish-yellow and the other dyestufi to dark blue.

The material is now immersedfor one minute in a developing bath of sodium-{5- naphtholate when the primuline becomes red, the new dyestufi remaining unchanged. After again rinsing to remove the excess of fi-naphtholate, the material is immersed for half-an-hour in a bath of a-naphthylamine ether, C H (OC I-I )'NH (2:1),' and then n washed. By this process the silk becomes black whilst the cotton remains red.

If a-naphthylamine ether is used for the first developer and resorcin for the second,

an orange silkpattern is obtained upon a blue cotton ground. Example 7'.

Acct l" silk yarn is dyed for an hour at about 075 C. from a bath containing 1 W g per cent of a dyestufi' of the formula which is obtained by coupling diazotized metanitraniline with dimethylaniline-omegasulphonic j acid (from monomethylanihne and sodium formaldehgxcjlie bisulphite). The bath is preferably ac'i ed with I per cent of formic acid or rendered alkaline with 1 per cent of soda ash. After washing off, the silk is dyed a bright yellow.

. I E wample 8. A fabric containing acetyl silk'is dyed as in the previous example, but using a dyestuff of the constitution I which is obtained by coupling diazotized dinitraniline with ethyl-aniline-methylomega-sulphonic acid (from mohoethylaniline and sodium formaldehyde bisulphite).

The acetyl silk is dyed crimson red.

Example 9.

L Acetyl silk yarn is dyed at 50 to 60 C.

ina bath containing 1 per cent of the compound of the constitution:

which is obtainable by combining diazotized para-nitraniline with aniline-ethyl-omegasulphonic acid, C H .NH.CH(CH ).SO H.

The bath may be employed neutral or rendered slightly alkaline or slightly acid. The

' silk acquires a bright orange shade.

Upon diazo'tization and development it gives the same range of shades as described in Example 4:.

: Example 10.

Acetyl silk-yarn is dyed at to 60 C. in a bath containing 1 per cent of thecompound of'the constitution:-

which may be obtained by reacting uponamido-azo benzene first with benzaldehyde and then with sodium bisulphite. The bath may be employed neutral or rendered slightly alkaline or slightly acid. The silk acquires a yellow shade which upon diazotization and development is converted into the following colours With dimethylanilineun u Bright scarlet. phenol Orange yellow. resorcinu Orangebrown.

fi-naphthol Ponceau.

fi oxynaphthoic acid Blui sh red.

Now what we claim is 1 In the dyeing, including printing, of acetyl cellulose, the process which comprises rendering an amido-azo dye soluble in water by a treatment of such dye with an aldehyde and a bisulfite and breaking up the new soluble combination so, formed'in the pres} once of the acetyl cellulose to be dyed.

2. The process of dyeing-including print meager ing-acetyl silk with an alkyl-omega-sulphonic acid, derived from an amido-azo compound, by .treating the acetyl silk with the dyestufi' in hot aqueous solution, whereby an aldehyde bisulphite compound is split off and the amido-azo compound is fixed on thefibre, substantially as described.

3. The process of' dyeing-including printing-acetyl, silk with an alkyl-omega sulphonic acid, derived from a primary amido-azo compound, by treating the acetyl silk with the dyestufi' in hot aqueous solution, whereby, an aldehyde bisulphite compound is split off and the amido-azo compound is fixed on the fibre, substantially as described.

4. 'The process sulphonic acid, derived from an amido-azo compound, by treating the acetyl silk with the dystuff in hot aqueous solution, whereby an aldehyde bisulphite compound is split off and the amido azo coinpoundv is fixed on the fibre, then diazotizing the amido-azo compound and treating with. a developer, substantially as described.

5. The process of dyeingincluding print ingacetyl silk with an alkyl-omega sulphonic acid, derived from a primary amido azo compound, by treating the acetyl silk with the dyestufl in hot aqueous solution, whereby an aldehyde bisulphite compound is split off and the amido-azo compound is fixed on the fibre, then diazotizing the ainidoazo compound and treating with a developer,

substantially as described.-'.

6. The process of-dyeing-including printingmaterial containing acetyl silk with an alkyl-omega sulphonic acid, derived froman amido-azo compound, by treating, the fibre or fabric with the dyestuff in hot aqueous solution, whereby an aldehyde bisulphite of dyeingincluding printing-acetyl silk with an alkyl-omega compound is split off and the amido-azo compound is fixed on the ade stantially as described. I

7. The process of dyeing-including printingi material containing acetyl silk with an silk, subalkyl-omega sulphonic acid, derived from a primary amido-azo compound, by treating the fibre or fabricwith the dyestuff in hot aqueous solution, whereby an aldehyde bi-' sulphite compound is split off and the amidoing--material containing acetyl silk with an alkyl-omega sulphonic acid, derived from a primary amido-azo compound, by treating the fibre or fabric with the dyestufi in hot aqueous solution, whereby an aldehyde bi sulphite compound is split off and the ainido-azo compound is fixed'on the aoetyi silk, then diazotizingqthe amido-azo compound and. treating with a developer, substantially as described.

10. The process of dyeing-including printingmaterial containing acetyl silk and other fibers, with a mixture of, an alkylome a sulphonic acid-derived from an ami o-azo compound--and another dyestufi whereby the amido-azo compound is fixed f on the acetyl silk, and the other dyestufi on the admixed fibre, substantially as described.

11. The process of dyeing including on the acetyl silk, and the other dyestuff on the admixed fibre, then diazotizing and treating with a developer, substantially as described.

In testimony whereof, we have hereunto 80 aflixed our signatures.

ARTHUR G. GREEN. KENNETH H. SAUNDERS. 

